Gelatinous Triblock Copolymer Elastomer Particles in Polyurethane Flexible Foams

ABSTRACT

Combinations of gelatinous elastomer and polyurethane foam may be made by introducing a plasticized triblock copolymer resin and/or a diblock copolymer resin at least partially cured into gel particles into a mixture of polyurethane foam forming components including a polyol and an isocyanate. The plasticized copolymer resin is polymerized to form a cured gelatinous elastomer or gel, which is then reduced in size, for instance to give an average particle size of 10 millimeters or less. Polymerizing the polyol and the isocyanate forms polyurethane foam. The polyurethane reaction is exothermic and can generate sufficient temperature to at least partially melt the styrene-portion of the triblock copolymer resin thereby extending the crosslinking and in some cases integrating the triblock copolymer within the polyurethane polymer matrix. The gel component has higher heat capacity than polyurethane foam and thus has good thermal conductivity and acts as a heat sink.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application from U.S. patentapplication Ser. No. 12/713,586 filed Feb. 26, 2010, which in turnclaims the benefit of U.S. provisional application No. 61/208,854 filedFeb. 27, 2009, both of which are incorporated herein by reference intheir entirety.

TECHNICAL FIELD

The invention relates to methods for compositions having plasticizedgelatinous triblock copolymer elastomers within polyether polyurethanefoams, polyester polyurethane flexible foams or latex foams and relatesto foams so made, and more particularly relates to plasticizedgelatinous triblock copolymer elastomer particles in polyether orpolyester polyurethane flexible foams or latex foams and methods formaking these materials. The invention more specifically relates tomattresses, pillows, bedding products, furniture upholstery, carpetpads, floor mats, shoe inserts, medical foams, seat cushions and backs,automotive foam, sports cushioning, transportation cushioning,headrests, arm rests and the like.

TECHNICAL BACKGROUND

Flexible polyurethane foam is commonly produced by methods of moldingand free-rise. The process of molding polyurethane flexible foaminvolves introducing chemicals required for making foam (in onenon-limiting embodiment, one or more polyols, one or more isocyanatesand one or more additives) in the desired ratio by injection or openpour into an individual, multiple or continuous mold and allowing thereacting foam system to fill the mold(s). There are many types offree-rise foam machines. Examples of these include, but are notnecessarily limited to, Open-Box Pouring Machines and Continuous FoamMachines such as Direct Lay-Down Machines and Maxfoam Process Machines.In a Continuous Direct Lay-down foam process, chemicals are metered andmixed through a mix-head and applied to a conveyed paper or film, uponwhich the foam chemicals react and rise as the mix is carried away fromthe lay-down area.

It is also well known to make gelatinous elastomer materials fromKRATON®, SEPTON®, or CALPRENE® triblock copolymer elastomers that havebeen plasticized with mineral oils or other non-aromatic oils.Gelatinous triblock copolymer elastomers have been produced as articlesand used in conjunction with prior and separately manufacturedpolyurethane or polyester foams, for instance as separate, discretelayers.

It is helpful and desirable to develop new, alternative and/or improvedfoams and methods for making the same that have combined and/or improvedproperties.

SUMMARY

There is provided in one non-limiting embodiment a combination ofgelatinous elastomer and polyurethane foam produced by the methodinvolving crosslinking a plasticized copolymer resin which may be atriblock copolymer resin, a diblock copolymer resin, and combinationsthereof, to give a cured gel. The method further involves reducing thesize of the cured gel into gel particles having an average particle sizeof about 10 millimeters or less. Additionally, the method includesintroducing the gelled particles into a mixture of polyurethane foamforming components which include a polyol and an isocyanate. The gelparticles are added in the range of about 0.1 to about 200 parts perhundred of the polyol component of polyurethane foam. The method alsoinvolves polymerizing the polyol and the isocyanate to form apolyurethane foam.

In a different non-restrictive version there is provided a combinationof gelatinous elastomer and open cell flexible polyurethane foamincluding cured gel particles comprising crosslinked plasticizedcopolymer resin selected from the group consisting of a triblockcopolymer resin, a diblock copolymer resin, and combinations thereof,the gel particles having an average particle size of about 10millimeters or less within an open cell flexible polyurethane foam. Thegel particles are present in the range of about 0.1 to about 200 partsper hundred of the polyol component of open cell flexible polyurethanefoam.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of a continuous, free-risepolyurethane foam processing apparatus;

FIG. 2 is a schematic illustration of a box-pour machine forpolyurethane foam;

FIG. 3 is a schematic illustration of an auger mixing system forplasticized gelatinous copolymer particles and polyol;

FIG. 4 is a schematic illustration of a mixing system for plasticizedgelatinous copolymer particles and polyol;

FIG. 5 is a graph of higher support factors at a compression greaterthan 50% plotting the ratio of IFD at specified % Compression relativeto 25% IFD as a function of % Compression;

FIG. 6 is a schematic illustration of a thermal conductivity testapparatus;

FIG. 7 is a photograph of an inventive white, soft open cell commodityviscoelastic flexible polyurethane foam having heterogeneouslydistributed gel particles; and

FIG. 8 is a microphotograph from one of the inventors' customers of acombination gelatinous elastomer-infused open cell flexible viscoelasticpolyurethane foam.

It will be appreciated that FIGS. 1-4 and 6 are schematic and that thevarious elements are not necessarily to scale or proportion, and thatmany details have been removed or simplified for clarity, and thus theinvention is not necessarily limited to the embodiments depicted in theFigures.

DETAILED DESCRIPTION

It has been discovered that in-situ incorporation of gelatinous triblockand/or diblock copolymer elastomer particles into open cell, flexiblepolyether or polyester polyurethane foam may be conducted while the foamis being produced. That is, the plasticized gelatinous copolymerparticles are incorporated in the polyurethane foam in-situ during thefoaming reaction using the exothermic heat of the foam reaction.Gelatinous triblock copolymer elastomers have been produced as articlesand used in conjunction with a prior and separately manufacturedpolyurethane or polyester foam as discrete, relatively large-scalecomponents or layers, but the methods and items made herein relate toincorporating the plasticized gelatinous triblock elastomers directlyinto the polyurethane foam structure while the polyurethane foam isproduced.

The reaction of the polyol/water and isocyanate to form polyurethanefoam is exothermic, and the heat from this exothermic reaction at leastpartially melts the triblock copolymer resin. In one acceptable,non-limiting embodiment, the triblock copolymer resin is essentiallycompletely polymerized prior to size reduction and incorporation intothe mixture of open cell, flexible polyurethane foam-forming components,such as a mixture of at least one polyol and at least one isocyanate.The resulting combination may have a marbled, mottled or spottedappearance of the gel within the polyurethane foam.

In another non-limiting embodiment, the gel particles are added in therange of about 0.1 to about 200 parts per hundred of the polyolcomponent of polyurethane foam. In an alternative, non-restrictiveversion, the gel particles are added in the range of about 5independently to about 50 parts per hundred of the polyol component ofpolyurethane foam. By independently is meant that any lower thresholdmay be combined with any upper threshold for an effective range herein.Further, the gel particles may be added in the range of about 30 partsper hundred of the polyol component.

The addition of the gel elastomer changes the temperature properties ofthe combination with the foam in a measurable way. The gel has higherheat capacity than does the open cell, flexible polyurethane foam, andthus acts as a heat sink. The gel is an excellent conductor of heat,better relative to polyurethane foam, and thus in combination with thefoam has the net effect of increasing the thermal conductivity of thegel-foam combination as compared to foam alone. When such a combinationis used in bedding materials, such as mattresses and pillows, the twofeatures combine to promote greater heat transfer and more comfortablesleep.

Since the gel is semi-liquid, it will deform, but not appreciablycompress. Thus, a gel-foam matrix has the very unique property of a“Variable Support Factor”. Support factor is defined by ASTM as theratio of the 65% and 25% IFD values. For typical viscoelastic foam, thisratio is about 2.0. As the gel-foam combination described herein iscompressed in small increments, the change in force required matches theunderlying foam until enough compression occurs to cause the gelparticles to contact one another. At this point, the gel-foam begins toact more like gel than foam and the resistance to compression increases.The point at which this transition occurs will vary with the content ofgel in the gel-foam matrix. A higher loading of gel results in the gelparticles interacting earlier in a compression cycle.

Polyurethane Component

As defined herein, the term polyurethane foam means polyether-basedpolyurethane foam or polyester-based polyurethane foam or a combinationpolyether and polyester polyurethane foam. As noted, polyurethane foamis commonly produced by methods of molding and free-rise. A commondesign for continuous free-rise processing equipment is the MAXFOAMmachine, available from Beamech Group Limited. This type of machine,schematically illustrated in FIG. 1, uses a trough 12 where thechemicals are first introduced from a mixing head 14. The foam chemicals(including, but not necessarily limited to, polyol(s), water, siliconesurfactant, catalyst, blowing agent(s), and isocyanate) stay in thetrough 12 for about 10 to 25 seconds and then spill over the trough liponto a series of fall-plates 16 leading to the main conveyor 18. Thefall-plates 16, side-walls (not shown) and conveyor(s) 18 are protectedfrom the reacting foam chemicals by a continuous film feed (bottom film,side films and additional films for block shaping; not shown in FIG. 1).Flexible polyurethane foam 20 is continuously produced by thistechnique.

Another common method of producing free-rise flexible foam is with abox-pour machine 30, as schematically illustrated in FIG. 2. This is abatch process whereby the foam chemicals are mixed and introduced in avariety of methods. These methods include but are not limited to thefollowing: a mix-head or injection cylinder 32 using metered chemicals,manual or automatic addition by weight, reaction-injection-molding (RIM)and injection cylinders are known methods of introducing the chemicalsinto a container 34 (box, mold or cylinder). The containers aretypically lined with cardboard or plastic film to facilitate removal ofthe foam 36.

It is believed that suitable open cell, flexible polyurethane foams arethose conventional polyether and polyester polyurethane foams or acombination polyether and polyester polyurethane foam. The “hydroxylnumber” for a polyol is a measure of the amount of reactive hydroxylgroups available for reaction. The value is reported as the number ofmilligrams of potassium hydroxide equivalent to the hydroxyl groupsfound in one gram of the sample. “Functionality” of a polyol is definedas the average number of hydroxyl groups per molecule.

The term “polyether polyol” includes linear and branched polyethers(having ether linkages) containing at least two hydroxyl groups, andincludes polyoxyethylene polyether polyols, polyoxypropylene polyetherpolyols or mixed poly(oxyethylene/oxypropylene)polyether polyols.Generally, polyethers are the polyoxyalkylene polyols, particularly thelinear and branched poly(oxyethylene) glycols, poly(oxypropylene)glycolsand their copolymers. Other alkylene oxides besides ethylene oxide andpropylene oxide may be used to produce suitable polyols. It will beappreciated that in the context herein the term “polyol” encompasses andincludes “polymer polyols” as those are generally defined in theindustry.

Polyols useful herein may have a functionality of 1.5 to 6.0 usingsingle or mixed initiators including but not limited to glycerin(glycerol), trimethylolpropane (TMP), propylene glycol (PG), dipropyleneglycol (DPG), ethylene glycol (EG), diethylene glycol (DEG),methylpropanediol (mpdiol), water, sucrose, D-sorbitol, glucoside,starch glycosides, aliphatic amines such as ethylenediamine (EDA),ethanolamine, diethanolamine (DEOA), triethanolamine,diisopropanolamine, erythritol, butane diol, hydrazine, low molecularweight adducts of polyfunctional amines, polyfunctional alcohols,aminoalcohols, alcoholamines and mixtures thereof, and aromatic aminessuch as aniline, toluene diamine, isomers of phenylene diamine, diethyltoluene diamine (DETA), pentaerythritol, isophorone diamine,2,4,6-triaminotoluene, diethyltolylene diamine, and mixtures thereof,and the like. Polyol designs herein may have mixed, blocked or acombination of mixed and blocked ethylene oxide (EO) and mixed, blockedor a combination of mixed and blocked propylene oxide (PO), or may bebased on natural sources or directly from natural sources such assoy-bean oil or castor-bean polyol.

The functionality or average functionality of a polyol should be takeninto consideration in designing the proper foam formulation forproducing polyurethane foam. In one non-limiting embodiment, the use oflow functionality (about 2) polyol is useful for the production ofviscoelastic foam. Where low functionality polyol(s) are used, a higherisocyanate index is generally required. The amount of isocyanateemployed is frequently expressed by the term “index” which refers to theratio of the total isocyanate used to the actual amount of isocyanaterequired for reaction with all of the active hydrogen-containingcompounds present in the reaction mixture, multiplied by 100. For mostfoam applications, the isocyanate index is in the range from 60 to 140.An isocyanate index below 100 is typically used for viscoelastic foam,soft and super-soft conventional foam and soft or super-soft highresilient, or HR foam. A non-limiting embodiment is the use ofviscoelastic foam as the carrier of the in-situ gel-foam. Open cell,flexible viscoelastic foam may be made using a wide range of polyols andisocyanates. For viscoelastic foam, polyol average functionalitiestypically range from about 2 to about 4, but may be higher in some casesand isocyanate functionalities range from about 2 to about 4, but may behigher in some cases. The isocyanate index used to produce viscoelasticfoam is determined by the desired properties and the functionality andequivalent weights of the polyol(s) and isocyanate(s) used in the foamformulation. In one non-limiting embodiment, viscoelastic foam used inthe production of gel-foam is made using a primary viscoelastic polyolwith a functionality of about 3 and an equivalent weight of about 1000and this is reacted with a blend of polymeric and di-functional MDI withan average functionality of about 2.3 at an index ranging from about 60to about 90. The formation of an in-situ gel-foam introducing gelparticles to polyurethane foam components for the co-formation of geland foam is possible using very wide range of polyurethane foam typesand formulations. The polyurethane foam formulations may include but arenot limited to the use of polyether polyol(s) alone or in combinationwith polyester polyol(s), grafted copolymer polyol(s), polymermodifiers, cross-linkers, chain extenders and plasticizers. In onenon-limiting embodiment, polyether polyol(s) are combined with polyesterpolyol(s) to achieve desired properties of the carrier foam. Many foamtypes were evaluated as carriers for in-situ gel-foam and it wasdiscovered that the embodied methods of producing in-situ gel-foam maybe applied to virtually any type of polyurethane foam, including but notlimited to, conventional foams, viscoelastic foams, high resilient (HR)foams, polyester foams and polyether-polyester blend foams all rangingin density from about 0.5 pcf to about 10 pcf and ranging in hardness asmeasured by the ASTM 25% IFD from about 3 to about 300.

Catalysts are used to control the relative rates of water-isocyanate(gas-forming) and polyol-isocyanate (gelling) reactions. The catalystmay be a single component, or in most cases a mixture of two or morecompounds. In one non-limiting embodiment, suitable catalysts forpolyurethane foam production are organotin salts and tertiary amines,used singly or together. The amine catalysts are known to have a greatereffect on the water-isocyanate reaction, whereas the organotin catalystsare known to have a greater effect on the polyol-isocyanate reaction.Total catalyst levels generally vary from 0 to about 5.0 parts by weightper 100 parts polyol. The amount of catalyst used depends upon theformulation employed and the type of catalyst, as known to those skilledin the art. Although various catalysts may be used in the methodsherein, control of the gelling catalyst level is critical to producingfoams with desired air permeability, which is a factor known tosignificantly affect foam cushioning performance. The following rangesof catalyst amounts may be satisfactory: amine catalyst from 0 to 2parts per 100 parts polyol; and organotin catalyst from 0 to 0.5 partsper 100 parts polyol.

One or more surfactants may also be employed in the foam-formingcomposition. The surfactants lower the bulk surface tension, promotenucleation of cells or bubbles, stabilize the rising cellular structureand emulsify incompatible ingredients. The surfactants typically used inpolyurethane foam applications are polysiloxane-polyoxyalkylenecopolymers, which may generally be used at levels between about 0.5 and3 parts by weight per 100 parts polyol. In the methods and compositionsherein, from 0 to 2 parts by weight per 100 parts polyol of surfactantmay be used, and alternatively 1 part by weight per 100 parts polyol.

A blowing agent may be included in the foam-forming composition. Acommon blowing agent is water that may be added in amounts from about0.1 to 7 parts per hundred parts polyol. Water acts as a blowing agentwhen it reacts with isocyanates and produces carbon dioxide, whichexpands the foam. In one non-limiting embodiment, water as a blowingagent is added in an amount suitable to achieve a desired foam density.Other blowing agents known as auxiliary blowing agents can be used incombination with water. However, the auxiliary blowing agent is notreacted in the foam matrix but instead acts as an inert expansion gas.

Cross-linking or chain-extending additives may be included in thefoam-forming composition to enhance processing, physical properties, andfoam stability. Typically, cross-linking or chain extending additivesare relatively small molecules containing 2 to 6 active hydrogen groups,or primary or secondary amine groups, and are added in amounts from 0 to10 parts per hundred parts polyol. Optional, representativecross-linking or chain-extending additives include, but are notnecessarily limited to, diethanolamine (DEOA), ethylene glycol (EG),diethylene glycol (DEG), propylene glycol (PG), dipropylene glycol(DPG), 1,4-butanediol (BDO), methyl-propane diol, glycerin and shortchain difunctional and polyfunctional polyether or polyester polyols. Inone optional, non-restrictive embodiment, the cross-linking additivesare included in amounts from 0.2 to 5.0 parts per hundred parts polyol.Alternatively however, the methods and compositions herein may bepracticed in the absence of a chain extender or cross-linking additives.

Optionally, other additives may be incorporated into the foam-formingcomposition. The optional additives include, but are not limited to,flame retardants, stabilizers, antimicrobial compounds, extender oils,dyes, pigments, and antistatic agents.

The open cell, flexible, viscoelastic foam described herein may beproduced under pressure or under vacuum using batch processes orcontinuous processes. Pressure can be applied by platens or conveyorswhich compress the foam while the foam is not fully cured.Alternatively, the method is practiced under atmospheric pressure, inthe regime of atmospheric pressure to greater than atmospheric pressure,or in the regime of atmospheric pressure to less than atmosphericpressure. The process may be a free rise process or may involve a moldas previously described.

Latex-Based Gel-Foam

It is expected that open cell, flexible latex foam could be used inplace of or in addition to polyurethane foam in combination withplasticized triblock copolymer gels to form unique latex gel-foam. Oneprocess used for open cell, flexible latex foam production involvesintroducing air into the latex, e.g. whipping or beating warm natural orsynthetic latex in the presence of additives to promote open cellformation, stabilization and curing. The additives may include, but notnecessarily be limited to, foam stabilizers, foam promoters, zinc oxidedelayed action gelling agents and combinations thereof. A final step inthis process is to cure the foam with heat. With the addition of gelparticles to the latex foam process, the heat applied to whip and curethe foam would also serve to partially or fully crosslink the gelparticles forming an integrated in situ open cell, flexible latexgel-foam.

Plasticized Elastomer Component

Plasticized triblock copolymer gels may be produced from high viscositytriblock copolymers and optionally with diblock copolymers that havebeen melted or mixed with a plasticizing agent, such as mineral oil,synthetic oil, etc., and optionally mixed with additives such ascolorants, polyols, etc. In other words, one non-limiting embodiment ofthe method involves gel particles (in a non-limiting example, aplasticized triblock gel polymer) that is made in the form of flowableor “fluffy” solid, which if heated sufficiently, would form a gel thatis added to the polyurethane foam components to produce the gel-foam. Inalmost all cases it is expected that the foaming reaction generatessufficient heat to melt the gel particles in the polyurethane foam.There may be cases where there is insufficient exothermic temperature tomelt the gel particles completely in the foam. The resulting gelparticles/foam would still have desirable properties, but the look andfeel of the gel particles/foam would be expected to be different.

Triblock copolymers include, but are not necessarily limited to, (SB)nstyrene-butadiene, (SEB)n, (SIS) styrene-isoprene-styrene blockcopolymers, (SEBS) styrene-ethylene-butylene-styrene block copolymers,(SEP) styrene-ethylene-propylene block copolymers, (SEEPS)styrene-ethylene-ethylene-propylene-styrene block copolymers, (SBS)styrene-butadiene-styrene block copolymers and the like. The term “n”here and elsewhere refers to the number of repeating polymer units. Thetriblock copolymers employed in the gel may have the more generalconfiguration of A-B-A. The A component represents a crystalline polymerend block segment of polystyrene; and the B component represents anelastomeric polymer center block segment. These “A” and “B” designationsare only intended to reflect conventional block segment designations.Elastomeric and polystyrene portions are incompatible and form atwo-phase system consisting of sub-micron domains of glassy polystyreneinterconnected by flexible elastomeric chains. These two discretedomains act as hard and soft block segments which help crosslink andreinforce the plasticized gelatinous triblock copolymer. This physicalelastomeric network structure is reversible, and heating the polymerabove the softening point of polystyrene temporarily disrupts thestructure, which can be restored by lowering the temperature below thesoftening point again. It may thus be understood that the copolymerresin or gel particle is optionally at least partially crosslinkedbefore, during or after introduction into the mixture of polyurethanefoam forming components. As noted, heating the copolymer resin via heatproduced by the reaction of the polyol and the polyisocyanate maypartially or completely crosslink the copolymer resin or gel particle.By “completely crosslink”, it is meant that crosslinking has occurred tothe maximum extent. However, it will be appreciated that it is notnecessary to completely crosslink the gel particle when it is reacted toform a gelatinous elastomer. That is, a successful product may result ifthe gelatinous elastomer is only partially crosslinked. Even if the gelparticle was fully or completely crosslinked, it is expected that theexothermic foam reactions would cause the gel to rearrange bonds and/orbecome physically attached to the foam, and in some cases chemicallyattached to the polyurethane components when active hydrogen components,such as polyols, are used as a plasticizer alone or in combination withone or more non-active hydrogen plasticizers or are used as a carrier inthe gel or gel particle. In the case where active hydrogen compounds areused, it would be expected that all or a portion of the active hydrogenswould react with polyisocyanate forming linkages with the polyurea,polyurethane and other components of the polyurethane foam.

In one non-limiting embodiment, the gel or gel particle is completelycured prior to addition to the polyurethane foam forming components. Inthis embodiment, a finished crosslinked gel is ground or cut intogranules or a powder and then added into the foam during production ofthe foam. There are many techniques and methods for reducing the size ofthe gelled polymer and this embodiment is not limited to any particularsize-reduction technique. In another non-restrictive version, thefinished gel, which may or may not be crosslinked, is a relatively veryfine grind (for instance particles having an average particle size ofabout 10 millimeters or less, alternatively 2 millimeters or less, sothat it may be dispersed in the foam to give a better feel and to avoidthe possibility of separating from the foam forming components duringthe foaming reaction. The ground particles may have an average volume ofbetween about 0.001 independently to about 1000 mm³, in anothernon-limiting version of between about 0.005 inde-pendently to about 125mm³, alternatively between about 0.01 independently to about 8 mm³.

Diblock copolymers of the general configuration A-B may also be usedalone or together with A-B-A triblock copolymers. Diblock copolymers aretypically used to modify the properties of a triblock copolymer. Themonomers suitable for use in diblock copolymers may be the same as thoseused in the triblock copolymers noted above.

Examples of copolymers that may be used to achieve one or more of thenovel properties herein are styrene-ethylene-butylene-styrene blockcopolymers (SEBS) under trade designations KRATON G1650, KRATON G 1651,KRATON G1652, and other like A-B-A triblock copolymers available fromKraton Performance Polymers. Other examples of suitable triblockcopolymer resins are available from Dynasol under trade designation ofCH-6110 and CH-6174.

Other grades of (SEBS) polymers may also be utilized herein providedsuch SEBS polymers exhibit the required properties. The styrene toethylene and butylene weight ratio of SEBS useful in forming thegelatinous elastomer may range from lower than about 20:80 to aboveabout 40:60. Typical ratio values for KRATON G1650, KRATON G 1651,KRATON G1652 are approximately about 30:70 to 33:67. These ratios mayvary broadly from the typical product specification values.

Plasticizers suitable for making acceptable gels are well known in theart, they include, but are not necessarily limited to, rubber processingoils such as paraffinic and naphthenic petroleum oils, highly refinedaromatic-free paraffinic and naphthenic food and technical grade whitepetroleum mineral oils, synthetic oils and natural oils and polyols madefrom natural oils and natural polyols. Synthetic oils are high viscosityoligomers such as non-olefins, isoparaffins, paraffins, aryl and/oralkyl phosphate esters, aryl and/or alkyl phosphite esters, polyols, andglycols. Many such oils are known and commercially available. Examplesof various commercially available oils include, but are not necessarilylimited to, PAROL® and TUFFLO® oils. Natural oils such as, but notlimited to, canola oil, safflower oil, sunflower oil, soybean oil,and/or castor oils may be used. Natural oil-based polyols arebiologically-based polyols such as, but not limited to, soybean-basedand/or castor bean polyols. The value of using polyols as plasticizersalone or together with other plasticizers is to provide the potentialfor chemical bonding of the gel particles with the polyurethane foamrather than just the physical bonding that occurs with non-reactiveplasticizers such as paraffinic or naphthenic mineral oils. This isbecause the polyols have active hydrogens. One advantage of usingpolyols as plasticizers or co-plasticizers is that the final combinedgel-foam may be less tacky and/or stronger than combined gel-foams madeonly with non-reactive plasticizers in the plasticized copolymer resin.The plasticizers described herein may also serve as carriers formodifying additives introduced into the gel or gel particles, such asphase transition additives, i.e. carriers to move an additive within thegel or gel particles and carriers used to transport an additive withinthe gel or gel particles. The plasticizer constitutes about 1independently to about 1,400 pph (parts per hundred parts of triblockcopolymer resin) and alternatively about 200 independently to about 800pph (parts per hundred parts of triblock copolymer resin), in a gelsuitable for in-situ polyurethane foaming is obtained.

The gel may also contain useful amounts of conventionally employedadditives such as stabilizers, antioxidants, antistatic agents,antimicrobial agents, ultraviolet stabilizers, phase change materials,surface tension modifiers such as silicone surfactants, emulsifyingagents, and/or other surfactants, grafting polyols, compatiblehydroxyl-containing chemicals which are completely saturated orunsaturated in one or more sites, solid or liquid fillers, antiblockingagents, colorants such as inorganic colorants, carbon black, organiccolorants or dyes, reactive organic colorants or dyes, fragrances, solidor liquid flame retardants, other polymers in minor amounts and the liketo an extent not affecting or substantially decreasing the desiredproperties of the combination of gelatinous elastomer and polyurethanefoam herein. Minor amounts of other polymers and copolymers may bemelt-blended with the styrene-ethylene-butylene-styrene block copolymersmentioned above without substantially decreasing the desired properties.Colorants may be added as is, or may be covalently reacted on thecopolymer backbone or fixed by pre-reacting, grafting, mechanical orchemical bonding compounds on the copolymer backbone and then fixing orbonding the color or dye on the grafted compound. Various organicmolecules may be used for this purpose including, but not necessarilylimited to, Milliken Polyurethane Dyes, Rebus pigments and dyes, andRYVEC pigments. The colorant is present in an amount up to about 50parts per hundred of the A-B-A triblock copolymer. Alternatively, thecolorant is used in the range of up to 2 pph of A-B-A triblockcopolymer. The gel may also be coated or premixed with detackifyingagents, such as melamine, calcium stearate, talc, and mixtures thereof,but not limited to the previously mentioned examples.

Gel Preparation

The plasticized triblock copolymer gel that is suitable for use inpolyurethane foams may be prepared by a method or methods includingbatch-wise or continuous mixing in a mixer, rotating vessel, ribbonblender, paddle blender, plough blender, plastic screw, or any otherequipment known in the art of skill that is used for mixing solids withadditives.

Alternatively, the plasticized gel may be prepared by mixingcontinuously in a mixer/auger system. A-B-A triblock copolymer resin,optional solvent, colorant, and plasticizer may be added and mixed withan auger with or without heat to produce a plasticized gel suitable forincorporation into polyurethane foam upon exiting the mixer/augersystem.

Alternatively, the plasticized gel may be prepared by adding all of thenecessary ingredients into a plastic screw and melt blending and/orextruding the melt mixture into a mold or through a screen that hasrotating blades/knives which cut the extruded pieces into fineparticles. These fine plasticized gel particles may be coated with anorganic powder such as melamine, an inorganic powder such as talc orfumed silica, or an oil to inhibit or prevent the particles fromsticking together. Alternatively, the un-plasticized resin orplasticized gel particle may be cryogenically ground by using liquid orsolid carbon dioxide, liquid nitrogen, or any other suitable cryogenicliquid to cool down the plastic to make the particle more brittle andable to grind to a controllable size. If carbon dioxide is used, thegrinding temperature can be as low as −110° F. (−79° C.). If liquidnitrogen is used, the grinding temperature can be as low as −321° F.(−196° C.).

The A-B-A triblock copolymer resin may be mixed with a plasticizer,optional solvent, colorant, or additives at a temperature between about−10° F. to about 400° F. (about −23° C. to about 204° C.) and at apressure from full vacuum to 20 atm (2 MPa).

One suitable method of making plasticized copolymer gel is by mixing theA-B-A triblock copolymer resin with a colorant. The colorant andcompatible solvent may also be premixed to aid in dispersing thecolorant throughout the resin. Other methods of dispersing the colorantmay be by heating the colorant and/or resin to reduce viscosity bytemperature or reducing viscosity in a compatible inert carrier.Suitable inert carriers include, but are not necessarily limited to,non-polar carriers, polar carriers, polyether polyol carriers, polyesterpolyol carriers, isocyanate/polyether prepolymers, liquid or solidfillers, liquid or solid flame retardants, water, and/or blowing agents.Another method is to use an A-B-A triblock copolymer with the desiredcolor already compounded in or fixed on the triblock copolymerelastomer. After the colorant has adequately coated the resin, anoptional solvent and plasticizer is/are added in the required weightratio relative to the resin. Suitable solvents include, but are notnecessarily limited to, the following examples: saturated acyclicaliphatic hydrocarbons, unsaturated acyclic aliphatic hydrocarbons,saturated cyclic aliphatic hydrocarbons, unsaturated cyclic aliphatichydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, alcohols,glycol ethers, ketones, aldehydes, epoxides, carboxylic acids, esters,glycol ether esters, fatty acids, phosphite esters, phosphate esters,dimethylsulfoxide, dimethylformamide, hexamethylphosphorotriamide,furan, water, methylene chloride, toluene, acetone and combinationsthereof. The solvent may be added in the range of from about 1 to about500 parts of triblock copolymer resin. The solvent can be added tosoften or melt some of the polystyrene units to swell the resin so theplasticizer can migrate into the resin more quickly. The solvent alsoaids in dispersing the colorant and helping the colorant to penetratethe resin and to help reduce colorant or dye leaching in the finalproduct. The solvent may remain in the gel or be evaporated from the gelor resin after colorant penetration or plasticizer addition. Onesuitable method is to remove the solvent prior to dispersing theprepared plasticized copolymer gel particles in the polyol blend.Heating alone or in combination with solvent will also help in theplasticizer penetration into the A-B-A triblock copolymer resin. Heatingthe final gel product increases the evaporation rate of the solvent fromthe gel. Heating the unplasticized resin or plasticized resin also helpsin fixing the colorant to reduce leaching and migration of color awayfrom the plasticized gel. One suitable but non-limiting embodiment forcoloration of the ABA triblock copolymer resin is to add dye using wateras a solvent, then after thorough mixing; the water is evaporatedleaving the dye as a coating and in some cases penetrating the ABAtriblock copolymer resin. The evaporation techniques may include, butare not limited to the use of heated air, vacuum, heated chamber,infrared heating or combinations thereof.

One method of adding gel particles to the compatible carrier is byaugering the gel particles 42 into a mix chamber 40 using auger 46, asschematically illustrated in FIG. 3, where the gel particles 42 andcompatible carrier 44 are mixed prior to adding other chemicals requiredto make polyurethane foam. Alternatively, mixing may be performeddirectly into the main mix head or can be mixed in a separate mix headand the gel particles and compatible carrier mixture fed into the mainmix head with the other formulation components. Another non-restrictivemethod may be to use the auger to mix the gel particles 42 andcompatible carrier together while augering to the main mix head. Anothernon-limiting embodiment of adding gel particles 42 to the compatiblecarrier 44 is by adding the gel particles into a compatible carrier in amix tank 50, as schematically illustrated in FIG. 4. A typical mix tank50 may have a heating/cooling jacket 52 for controlling the temperaturewithin the tank. The carrier is added to the mixing tank and then thegel particles 42 is mixed into the carrier while agitating. Whilemixing, the gel particles 42 may be added to the tank gradually or allat once. Alternatively, the gel particles 42 may be added to the mixingtank first and then the compatible carrier added to the tank whilemixing. It will be appreciated that the method described herein is notlimited to these two examples, since there are many combinations forcombining gel particles with a compatible carrier before incorporatinggel particles into final polyurethane foam.

Applications of the Combined Gel Elastomer and Polyurethane Foams

The list below shows some, but not all, of the applicable uses of thecombination of gelatinous elastomer and open cell flexible polyurethanefoam or latex foam produced by the methods herein.

-   -   1. Mattresses, pillows, and bed-top products;    -   2. General furnishings and Upholstered furniture including        cushions, armrests, seat-backs, foot-rests, decorative        cushioning and functional support.    -   3. Rebond carpet pad or use as a floor mat (rebond carpet pad        uses recycled foam to create the pad that goes under carpet,        giving a cushioned feel and extra life to the carpet);    -   4. Use as a shoe insert foamed in-situ with energy absorption        foam, viscoelastic foam or other foam;    -   5. Use in medical applications such as wheelchair seat cushions        and backs, orthopedic shoes, hospital beds, gurney pads, medical        bed pads, medical supports and cushioning;    -   6. Use in conventional polyether polyurethane foams, high        resilient polyether polyurethane foams, viscoelastic polyether        polyurethane foams, semi-rigid polyether polyurethane foams,        rigid polyether polyurethane foams, polyester polyurethane        foams, combined polyether-polyester foam or latex foam for        general cushioning, energy absorption, packaging, sealants and        fillers; and    -   7. Seat cushions, seat backs, headrests and armrests of chairs        and seats for application in vehicles such as automobiles,        motorcycles, bicycles, buses, aircraft, watercraft, tractors and        other agricultural equipment such as combines, construction        equipment and utility vehicles.

One suitable application of the methods and compositions herein includesincorporating the triblock copolymer gel in viscoelastic polyurethanefoam. The triblock copolymer gel, optionally in combination with acarrier, may be added to the unreacted polyurethane components andincorporated in the open cell, flexible viscoelastic polyurethane foam.Adding triblock copolymer gel to viscoelastic polyurethane gel mayresult in higher support factors, higher thermal conductivity, andhigher heat capacity.

The flexible polyurethane foams or latex foams with the in-situ formedgelatinous elastomer described herein may find utility in a very widevariety of applications. More specifically and other in non-limitingembodiments, the combined polymers would be suitable as pillows orpillow components, including, but not necessarily limited to, pillowwraps or shells, pillow cores, pillow toppers, for the production ofmedical comfort pads, medical mattresses and similar comfort and supportproducts, and residential/consumer mattresses mattress toppers, andsimilar comfort and support products, typically produced withconventional flexible polyurethane foam or fiber. All of these uses andapplications are defined herein as “bedding products”. Alternatively,the combination in-situ formed gelatinous elastomer/open cell flexiblepolyurethane foams described herein are expected to be useful for theproduction of upholstered furniture to replace conventional foam,polyester fiber or other support materials. Examples of theseapplications include but are not limited to upholstered chair backs,head-rests, foot-rests, arm-rests, neck supports, quilting support andcushioning and the like and combinations thereof. All of these latteruses and applications are defined herein as “furniture upholstery”.

The invention will now be described more specifically with respect toparticular formulations, methods and compositions herein to furtherillustrate the invention, but which examples are not intended to limitthe methods and compositions herein in any way. Table 1 and 2 presentssixteen formulation examples of open cell polyurethane flexible foamsmade according to the methods described herein. Foam properties arepresented in the lower portion of Tables 1 and 2. The componentdefinitions and plasticized gelatinous triblock polymer descriptions aregiven in Table 3.

TABLE 1 FORMULATION EXAMPLES - POLYURETHANE FLEXIBLE FOAMS Sample #Units 5504 5513 6051 6052 6053 6054 6057 6058 X-48 pph 100 X-49 pph 100X-50 pph 100 100 100 100 100 100 Water Total pph 1.77 1.82 2.25 2.252.25 2.25 2.25 2.25 L-618 pph 0.8 0.8 1.4 1.4 1.4 1.4 1.4 1.4 A-133 pph0.5 ZF-10 pph 0.1 0.16 0.16 0.16 0.16 0.16 0.16 T-Cat 110 pph 0.08 0.060.10 0.10 0.10 0.10 0.10 0.10 Gel #14 pph 30.0 Gel #18 pph 30.0 Gel #24pph 30.0 30.0 Gel #25 pph 30.0 Gel #26 pph 30.0 Gel #27 pph 30.0 MDI pph48.2 46.88 47.72 47.72 47.72 47.72 47.72 47.72 Cream Time sec 21 40 2426 26 26 26 25 Rise Time sec 127 200 129 166 170 175 173 173 Settleinches 0 0 0 0 0 0 0 0 Density pcf 4.56 5.05 3.11 3.98 3.97 3.96 3.963.96 Airflow¹ SCFM 2.9 3.4 3.6 3.8 4.8 4.9 4.2 4.6 25% IFD² Lbf/50 in²6.2 19.1 12.3 10.4 7.6 7.8 8.4 8.3 ¹Airflow: ASTM D 3574 G ²25% IFD:ASTM D 3574 B

TABLE 2 FORMULATION EXAMPLES - POLYURETHANE FLEXIBLE FOAMS Sample #Units 6702 6703 6704 6705 6706 6707 6708 6709 X-51 pph 100 100 100 100100 100 100 100 Water Total pph 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10L-618 pph 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 ZF-10 pph 0.20 0.200.20 0.20 0.20 0.20 0.20 0.20 T-Cat 110 pph 0.12 0.12 0.12 0.12 0.120.12 0.12 0.12 Gel #30 pph 30.0 Gel #31 pph 30.0 Gel #32 pph 30.0 Gel#33 pph 30.0 Gel #34 pph 30.0 Gel #35 pph 30.0 Gel #36 pph 30.0 Gel #37pph 30.0 MDI pph 47.8 47.8 47.8 47.8 47.8 47.8 47.8 47.8 Cream Time sec21 22 22 20 22 28 22 23 Rise Time sec 148 156 161 155 158 257 140 155Settle inches 0 0 0 0 0 2 0 0 Density pcf 4.15 4.27 4.21 4.34 4.23 5.214.16 4.34 Airflow¹ SCFM 2.8 3.5 4.0 3.5 3.9 8.7 2.6 4.1 25% IFD² Lbf/50in² 21.0 16.1 14.1 13.9 13.9 5.3 23.2 14.9 ¹Airflow: ASTM D 3574 G ²25%IFD: ASTM D 3574 B

TABLE 3 COMPONENT DEFINITIONS X-48 Polyol Blend from Peterson ChemicalTechnology, OH 169.7 X-49 Polyol Blend from Peterson ChemicalTechnology, OH 157.3 X-50 Polyol Blend from Peterson ChemicalTechnology, OH 148.4 X-51 Polyol Blend from Peterson ChemicalTechnology, OH 145.6 F3222 3200 MW Conventional Polyol from Bayer, 52.0OH A-133 23% bis(dimethylaminoethyl)ether in 3000 MW polyol ZF-10Reactive catalyst available from Huntsman Chemicals L-618 Siliconesurfactant available from Momentive Performance Materials MDI PolymericMDI having a NCO content of about 32.6% with an average functionality ofabout 2.4 T-Cat Stannous octoate catalyst available from GulbrandsenChemicals 110 Gel #14 (Plasticized Gelatinous Triblock Copolymer) Add82.47 grams Kraton G1651H Add 1.03 grams Milliken X17AB Add 45.91 gramsAcetone Evaporated to 1.12 gram acetone Added 372.22 grams ofhydrogenated paraffinic oil Gel #18 (Plasticized Gelatinous TriblockCopolymer) Add 100.44 grams Kraton G1651H Add 1.14 grams Milliken X17ABAdd 55.9 grams Acetone Add 446.80 grams of hydrogenated paraffinic oilEvaporated acetone Gel #24 (Plasticized Gelatinous Triblock Copolymer)Add 174.15 grams Kraton E1830 Add 1.99 grams Milliken X17AB Add 35.51grams Acetone Add 530.5 grams of hydrogenated paraffinic oil Evaporatedacetone Gel #25 (Plasticized Gelatinous Triblock Copolymer) Add 132.67grams Kraton G1651H Add 1.53 grams Milliken X17AB Add 27.44 gramsAcetone Add 577.73 grams of hydrogenated paraffinic oil Evaporatedacetone Gel #26 (Plasticized Gelatinous Triblock Copolymer) Add 132.85grams Kraton E1830 Add 1.57 grams Milliken X17AB Add 40.06 grams AcetoneAdd 581.92 grams of hydrogenated paraffinic oil Evaporated acetone Gel#27 (Plasticized Gelatinous Triblock Copolymer) Add 132.01 grams KratonE1830 Add 1.55 grams Milliken X17AB Add 52.8 grams Acetone Add 578.34grams of hydrogenated paraffinic oil Evaporated acetone Gel #30(Plasticized Gelatinous Triblock Copolymer) Add 130.5 grams of KratonG1651H Add 68.95 grams of Water-based dye Evaporate water away at 230deg F. Add 559.7 grams of hydrogenated paraffinic oil Mix Gel #31(Plasticized Gelatinous Triblock Copolymer) Add 130.6 grams of KratonG1651H Add 34.5 grams of Colorant (low-water dye) Evaporate water awayat 230 deg F. Add 561.1 grams of hydrogenated paraffinic oil Mix Gel #32(Plasticized Gelatinous Triblock Copolymer) Add 130.6 grams of KratonG1651H Add 30.4 grams of Colorant (low-water dye with fixing additive)Evaporate water away at 230 deg F. Add 561.1 grams of hydrogenatedparaffinic oil Mix Gel #33 (Plasticized Gelatinous Triblock Copolymer)Add 130.6 grams of Kraton G1651H Add 27.2 grams of Colorant (no-waterdye) Evaporate water away at 230 deg F. Add 561.1 grams of hydrogenatedparaffinic oil Mix Gel #34 (Plasticized Gelatinous Triblock Copolymer)Add 48.83 grams of Kraton G1651H Add 25.88 grams of Water-based dyeEvaporate water away at 230 deg F. Add 6.45 grams of Soybean-basedpolyol and 208.6 grams of hydrogenated paraffinic oil Mix Gel #35(Plasticized Gelatinous Triblock Copolymer) Add 48.83 grams of KratonG1651H Add 25.88 grams of Water-based dye Evaporate water away at 230deg F. Add 43.0 grams of Canola Oil and 172.0 grams of hydrogenatedparaffinic oil Mix Gel #36 (Plasticized Gelatinous Triblock Copolymer)Add 48.83 grams of Kraton G1651H Add 25.88 grams of Water-based dyeEvaporate water away at 230 deg F. Add 215.0 grams of hydrogenatedparaffinic oil Mix Gel #37 (Plasticized Gelatinous Triblock Copolymer)Add 48.83 grams of Kraton G1651H Add 25.88 grams of Water-based dyeEvaporate water away at 230 deg F. Add 37.6 grams of X28 (phase changeadditive from Peterson Chemical Technology) and 177.4 grams ofhydrogenated paraffinic oil Mix

Higher Support Factors

One advantage of the method described herein in producing open cellflexible foam is that it gives the foam higher support factors than afoam without the triblock copolymer elastomer. A sample with dimensionsof 4″ wide×7.25″ long×2″ high was compressed on an IFD instrument. Thesample was tested at 25%, 40%, 50%, 60%, 70%, 80%, 85%, 90% and 90%compression. At each compression setting, the force was allowed to relaxfor 60 seconds before the force was recorded. Table 4 shows thecompression forces for each compression percentage exhibited by fourfoam samples reported in Table 1. FIG. 5 shows the data graphically. Thecontrol sample 6051 without any gelatinous elastomer had a supportfactor of 1.95 at 65% compression relative to 25% compression. Thegel-containing Viscoelastic foams had support factors considerably abovethis. For non-gel polyurethane foam, the 65%-to-25% support factor istypically in the range of 1.9-2.2. With 30 pph of gel added, the supportfactor increased to 2.6-3.1 for the 65% compression relative to 25%compression. The rate of change of the force required to compressgel-foam as a function of the percent compression is relative to theparts of gel per hundred parts of Polyol (pph) used in the in-situgel-foam formulation. Increasing the loading of gel in gel-foam willgenerally increase the rate of change of support factor (ΔSF∝dF/dC,where SF=support factor, F=Compression Force and C=CompressionPercentage).

TABLE 4 HIGHER COMPRESSION FORCE TESTING 6051 6052 6053 6054 Units %Compression lbf lbf lbf lbf 25% 4.75 3.22 2.19 2.57 40% 5.58 4.19 2.973.4 50% 6.47 5 4.03 4.23 60% 8.11 7.07 5.68 5.81 70% 11.82 11.64 9.4910.01 80% 24.06 27.38 23.61 24.13 85% 43.09 54 47.05 47.6 90% 105.08146.28 129.44 130.03

Improved Thermal Conductivity

Another advantage of the methods and compositions herein is animprovement in the thermal conductivity or heat transfer properties. Athermal conductivity apparatus 60 was built according to FIG. 6. A foamsample 62 is placed between two ½″ thick acrylic plates 64 bounded oneither side by 1″ thick polystyrene board 66 and 1½″ plastic spacers 68.The apparatus 60 is capped on the top and bottom by ¼″ aluminum plates70 and a silicone heater pad 72 is located on the bottom of thelowermost aluminum plate 70. Four Type K thermocouples 74 are located inthe center on each side of the acrylic plates 64 with a known distanceof each thermocouple from each edge.

The thermal conductivities for a non-gel foam sample (Sample 6051) and agel-foam sample (Sample 6052) were tested. The 3-inch thick samplethickness was compressed to 0.5 inches to remove air pockets in thefoam. Table 5 shows the test results and the calculated thermalconductivity for each foam sample tested. The gel foam sample (Sample6052) showed a 29.2% improvement in thermal conductivity relative to thecontrol non-gel sample (Sample 6051).

TABLE 5 THERMAL CONDUCTIVITY RESULTS Control 6051 - 3″ thick compressedto 0.5″ Centerline hole from edge: 0.094″ Inlet Outlet Delta Thickness KArea Resistance Temp Temp Temp in. Btu/(hr-ft° F.) ft² (hr-° F.)/Btu °F. ° F. ° F. Acrylic 0.285 0.1135 0.085 2.460 201 193.4 7.65 Acrylic0.094 0.1135 0.085 0.811 193.4 190.8 2.52 Control 0.5 0.0226 0.08521.657 190.8 123.5 67.35 6051 Acrylic 0.094 0.1135 0.085 0.811 123.5120.9 2.52 Acrylic 0.285 0.1135 0.085 2.460 120.9 113.3 7.65 Total DeltaTemp 87.7° F. Total Heat Flow 3.11 Btu/hr Gel 6052 - 3″ thick compressedto 0.5″ Centerline hole from edge: 0.094″ Inlet Outlet Delta Thickness KArea Resistance Temp Temp Temp in. Btu/(hr-ft° F.) ft² (hr-° F.)/Btu °F. ° F. ° F. Acrylic 0.285 0.1135 0.085 2.460 186.3 178.0 8.35 Acrylic0.094 0.1135 0.085 0.811 178.0 175.2 2.75 Gel 0.5 0.0292 0.085 16.759175.2 118.3 56.89 6052 Acrylic 0.094 0.1135 0.085 0.811 118.3 115.5 2.75Acrylic 0.285 0.1135 0.085 2.460 115.5 107.2 8.35 Total Delta Temp 79.1°F. Total Heat Flow 3.39 Btu/hr % Increase in Thermal Conductivitybetween Gel-foam Foam Sample 6052 and Non-gel Foam Sample 6051: 29.2%

Improved Heat Capacity

Open cell, flexible polyurethane foams produced with in-situ gel or gelparticles are also expected to have higher heat capacity than non-gelpolyurethane foams. This property is important when the polyurethanefoams with in-situ gel are used in bedding products. Higher heatcapacity in combination with higher thermal conductivity will transferheat away from the contact surface between a person and the foam. Thefoam will thus have a cooler feel for a person in contact with the foam.

Many modifications may be made in the methods of and implementation ofthis invention without departing from the spirit and scope thereof thatare defined only in the appended claims. For example, the exact triblockcopolymer resin, diblock copolymer resin, gel additives, gel particles,polyols, isocyanates, catalysts and additives used may be different fromthose used explicitly mentioned or suggested here. Additionally,techniques and methods for improving the properties and/or processingcharacteristics of combinations of gelatinous elastomers andpolyurethane foams other than those specifically mentioned may findutility in the methods herein. Various combinations of triblock and/ordiblock gelatinous elastomer resins, polyols, isocyanates, catalysts andadditives, and processing pressures besides those explicitly mentionedherein are expected to be useful.

The words “comprising” and “comprises” as used throughout the claims isinterpreted “including but not limited to”.

The present invention may suitably comprise, consist or consistessentially of the elements disclosed and may be practiced in theabsence of an element not disclosed. For instance, a combination ofgelatinous elastomer and open cell flexible polyurethane foam may beproduced by a method consisting of or consisting essentially ofcrosslinking a plasticized copolymer resin selected from the groupconsisting of a triblock copolymer resin, a diblock copolymer resin, andcombinations thereof, to give a cured gel; reducing the size of thecured gel into gel particles having an average particle size of about 10millimeters or less; introducing the gelled particles into a mixture ofpolyurethane foam forming components comprising a polyol and anisocyanate; and polymerizing the polyol and the isocyanate to form anopen cell flexible polyurethane foam; where the gel particles are addedin the range of about 0.1 to about 200 parts per hundred of the polyolcomponent of open cell flexible polyurethane foam.

Additionally there may be provided a combination of gelatinous elastomerand open cell flexible polyurethane foam consisting of or consistingessentially of cured gel particles comprising crosslinked plasticizedcopolymer resin selected from the group consisting of a triblockcopolymer resin, a diblock copolymer resin, and combinations thereof,the gel particles having an average particle size of about 10millimeters or less within an open cell flexible polyurethane foam;where the gel particles are present in the range of about 0.1 to about200 parts per hundred of the polyol component of open cell flexiblepolyurethane foam.

What is claimed is:
 1. A combination of gelatinous elastomer and opencell flexible polyurethane foam produced by the method comprising:crosslinking a plasticized copolymer resin selected from the groupconsisting of a triblock copolymer resin, a diblock copolymer resin, andcombinations thereof, to give a cured gel; reducing the size of thecured gel into gel particles having an average particle size of about 10millimeters or less; introducing the gelled particles into a mixture ofpolyurethane foam forming components comprising a polyol and anisocyanate; and polymerizing the polyol and the isocyanate to form anopen cell flexible polyurethane foam; where the gel particles are addedin the range of about 0.1 to about 200 parts per hundred of the polyolcomponent of open cell flexible polyurethane foam.
 2. The combination ofclaim 1 wherein the copolymer resin is at least partially melted by heatproduced by polymerizing the polyol and the isocyanate to form the opencell flexible polyurethane foam.
 3. The combination of claim 1 where thecopolymer resin is a triblock copolymer resin and the copolymer resin isadded in the range of about 0.1 to about 200 parts per hundred of thepolyol component of open cell flexible polyurethane foam.
 4. Thecombination of claim 1 where the copolymer resin is formed bycompounding a copolymer with at least one plasticizing oil andoptionally a component selected from the group consisting of colorants;solvents; elastomeric diblock copolymer; antioxidants; antistaticagents; antimicrobial agents; flame retardants; ultraviolet stabilizers;phase change materials; surface tension modifiers; emulsifying agents;surfactants; fragrances; active hydrogen-containing components selectedfrom the group consisting of primary amines, secondary amines, primaryhydroxyls, secondary hydroxyls and combinations thereof; solid fillers;liquid fillers; and combinations thereof.
 5. The combination of claim 4where the copolymer resin comprises a colorant selected from the groupconsisting of inorganic pigment, carbon black, organic colorant, organicdye, reactive colorant, reactive dye and combinations thereof, and wherethe colorant is present in an amount up to about 50 parts per hundred ofthe copolymer resin.
 6. The combination of claim 4 where the copolymerresin comprises a solvent selected from the group consisting ofsaturated acyclic aliphatic hydrocarbons, unsaturated acyclic aliphatichydrocarbons, saturated cyclic aliphatic hydrocarbons, unsaturatedcyclic aliphatic hydrocarbons, aromatic hydrocarbons, chlorinatedhydrocarbons, alcohols, glycol ethers, ketones, aldehydes, epoxides,carboxylic acids, esters, glycol ether esters, fatty acids, phosphiteesters, phosphate esters, dimethylsulfoxide, dimethylformamide,hexamethylphosphorotriamide, furan, water, methylene chloride, toluene,acetone and combinations thereof.
 7. The combination of claim 4 wherethe plasticizing oil is selected from the group consisting of aparaffinic mineral oil, naphthenic mineral oil, synthetic oil producedfrom polybutenes, polypropenes, polyterpenes, paraffins, isoparaffins,polyols, polyoxyalkyleneamines, glycols, soybean-based polyols, castorbean-based polyols, canola oil, safflower oil, sunflower oil, soybeanoil, castor oil and combinations thereof, and the plasticizing oil ispresent in the range of from about 1 to about 1400 parts per hundred ofcopolymer resin.
 8. The combination of claim 1 where the copolymer resinis a triblock copolymer resin selected from the group consisting ofstyrene-ethylene-butylene-styrene (SEBS),styrene-ethylene-propylene-styrene (SEPS),styrene-ethylene-ethylene-propylene-styrene (SEEPS),styrene-isoprene-styrene (SIS) and combinations thereof; and theelastomeric diblock copolymer, if present, is selected from the groupconsisting of styrene-ethylene-propylene (SEP),styrene-ethylene-butylene (SEB), styrene-ethylene-ethylene (SEE),styrene-isoprene (SI) and combinations thereof.
 9. The combination ofclaim 1 where the copolymer resin further comprises an inert carrierselected from the group consisting of non-polar carriers, polarcarriers, polyether polyol carriers, isocyanate/polyether prepolymers,liquid or solid fillers, liquid or solid flame retardants, and/orblowing agents.
 10. The combination of claim 1 where the gelledparticles have an average volume between about 0.001 and about 1000 mm³.11. An article of manufacture comprising the combination of gelatinouselastomer and open cell flexible polyurethane foam of claim 1, where thearticle is selected from the group consisting of rebond carpet pads,floor mats, shoe inserts, medical foams, mattresses, pillows, beddingproducts, seat cushions, seat backs, head rests, armrests andcombinations thereof.
 12. An article of manufacture comprising thecombination of gelatinous elastomer and open cell flexible polyurethanefoam of claim 1 where the polyurethane foam is selected from the groupconsisting of polyether polyurethane foam, high-resiliency polyetherpolyurethane foam, viscoelastic polyether polyurethane foam, andcombinations thereof.
 13. The article of manufacture of claim 12 wherethe article of manufacture is produced employing a technique selectedfrom the group consisting of free rise, molded, and combinationsthereof.
 14. An article of manufacture comprising the combination ofgelatinous elastomer and open cell flexible polyurethane foam of claim 1wherein the combination of gelatinous elastomer and polyurethane foam islayered with at least one other material selected from the groupconsisting of: a flexible viscoelastic foam, a flexible resilientpolyurethane foam; a flexible high resilient (HR) foam, a latex foam,and combinations thereof.
 15. The article of manufacture of claim 14selected from the group consisting of mattresses, bedding products,pillows, furniture cushioning, wheelchairs, medical pads, medicalsupports, sports equipment, transportation seating and combinationsthereof.
 16. A combination of gelatinous elastomer and open cellflexible polyurethane foam comprising: cured gel particles comprisingcrosslinked plasticized copolymer resin selected from the groupconsisting of a triblock copolymer resin, a diblock copolymer resin, andcombinations thereof, the gel particles having an average particle sizeof about 10 millimeters or less within an open cell flexiblepolyurethane foam; where the gel particles are present in the range ofabout 0.1 to about 200 parts per hundred of the polyol component of opencell flexible polyurethane foam.
 17. The combination of claim 16 whereinat least a portion of the cured gel particles are at least partiallymelted within the open cell flexible polyurethane foam.
 18. Thecombination of claim 16 where the copolymer resin is a triblockcopolymer resin.
 19. The combination of claim 16 where the copolymerresin is formed by compounding a copolymer with at least oneplasticizing oil and optionally a component selected from the groupconsisting of colorants; solvents; elastomeric diblock copolymer;antioxidants; antistatic agents; antimicrobial agents; flame retardants;ultraviolet stabilizers; phase change materials; surface tensionmodifiers; emulsifying agents; surfactants; fragrances; activehydrogen-containing components selected from the group consisting ofprimary amines, secondary amines, primary hydroxyls, secondary hydroxylsand combinations thereof; solid fillers; liquid fillers; andcombinations thereof.
 20. The combination of claim 19 where thecopolymer resin comprises a solvent selected from the group consistingof saturated acyclic aliphatic hydrocarbons, unsaturated acyclicaliphatic hydrocarbons, saturated cyclic aliphatic hydrocarbons,unsaturated cyclic aliphatic hydrocarbons, aromatic hydrocarbons,chlorinated hydrocarbons, alcohols, glycol ethers, ketones, aldehydes,epoxides, carboxylic acids, esters, glycol ether esters, fatty acids,phosphite esters, phosphate esters, dimethylsulfoxide,dimethylformamide, hexamethylphosphorotriamide, furan, water, methylenechloride, toluene, acetone and combinations thereof.
 21. The combinationof claim 19 where the plasticizing oil is selected from the groupconsisting of a paraffinic mineral oil, naphthenic mineral oil,synthetic oil produced from polybutenes, polypropenes, polyterpenes,paraffins, isoparaffins, polyols, polyoxyalkyleneamines, glycols,soybean-based polyols, castor bean-based polyols, canola oil, saffloweroil, sunflower oil, soybean oil, castor oil and combinations thereof,and the plasticizing oil is present in the range of from about 1 toabout 1400 parts per hundred of copolymer resin.
 22. The combination ofclaim 19 where the copolymer resin is a triblock copolymer resinselected from the group consisting of styrene-ethylene-butylene-styrene(SEBS), styrene-ethylene-propylene-styrene (SEPS),styrene-ethylene-ethylene-propylene-styrene (SEEPS),styrene-isoprene-styrene (SIS) and combinations thereof; and theelastomeric diblock copolymer, if present, is selected from the groupconsisting of styrene-ethylene-propylene (SEP),styrene-ethylene-butylene (SEB), styrene-ethylene-ethylene (SEE),styrene-isoprene (SI) and combinations thereof.
 23. The combination ofclaim 16 where the gelled particles have an average volume between about0.001 and about 1000 mm³.
 24. An article of manufacture comprising thecombination of gelatinous elastomer and open cell flexible polyurethanefoam of claim 16, where the article is selected from the groupconsisting of rebond carpet pads, floor mats, shoe inserts, medicalfoams, mattresses, pillows, bedding products, seat cushions, seat backs,head rests, armrests and combinations thereof.
 25. An article ofmanufacture comprising the combination of gelatinous elastomer and opencell flexible polyurethane foam of claim 16 where the polyurethane foamis selected from the group consisting of polyether polyurethane foam,high-resiliency polyether polyurethane foam, viscoelastic polyetherpolyurethane foam, and combinations thereof.
 26. The article ofmanufacture of claim 25 where the article of manufacture is producedemploying a technique selected from the group consisting of free rise,molded, and combinations thereof.
 27. An article of manufacturecomprising the combination of gelatinous elastomer and open cellflexible polyurethane foam of claim 16 wherein the combination ofgelatinous elastomer and polyurethane foam is layered with at least oneother material selected from the group consisting of: a flexibleviscoelastic foam, a flexible resilient polyurethane foam; a flexiblehigh resilient (HR) foam, a latex foam, and combinations thereof. 28.The article of manufacture of claim 27 selected from the groupconsisting of mattresses, bedding products, pillows, furniturecushioning, wheelchairs, medical pads, medical supports, sportsequipment, transportation seating and combinations thereof.
 29. Acombination of gelatinous elastomer and open cell flexible polyurethanefoam produced by the method comprising: cured gel particles comprisingcrosslinked plasticized copolymer resin selected from the groupconsisting of a triblock copolymer resin, a diblock copolymer resin, andcombinations thereof, the gel particles having an average particle sizeof about 10 millimeters or less within an open cell flexiblepolyurethane foam; where: the gel particles are present in the range ofabout 0.1 to about 200 parts per hundred of the polyol component of opencell flexible polyurethane foam; where at least a portion of the curedgel particles are at least partially melted within the open cellflexible polyurethane foam; and where the copolymer resin is a triblockcopolymer resin selected from the group consisting ofstyrene-ethylene-butylene-styrene (SEBS),styrene-ethylene-propylene-styrene (SEPS),styrene-ethylene-ethylene-propylene-styrene (SEEPS),styrene-isoprene-styrene (SIS) and combinations thereof; and theelastomeric diblock copolymer, if present, is selected from the groupconsisting of styrene-ethylene-propylene (SEP),styrene-ethylene-butylene (SEB), styrene-ethylene-ethylene (SEE),styrene-isoprene (SI) and combinations thereof.